US11905607B2 - Pure-H2O-fed electrocatalytic CO2 reduction to C2H4 beyond 1000-hour stability - Google Patents
Pure-H2O-fed electrocatalytic CO2 reduction to C2H4 beyond 1000-hour stability Download PDFInfo
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- US11905607B2 US11905607B2 US17/806,102 US202217806102A US11905607B2 US 11905607 B2 US11905607 B2 US 11905607B2 US 202217806102 A US202217806102 A US 202217806102A US 11905607 B2 US11905607 B2 US 11905607B2
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Definitions
- the present invention relates to a pure-H 2 O-fed electrolysis system for electrocatalytic CO 2 reduction (ECO 2 R).
- the present invention provides a pure-H 2 O-fed membrane-electrode assembly (MEA) electrolysis system under an industrial applicable continuous flow condition for ECO 2 R-to-C 2 H 4 /C 2+ compounds using a high-performance step-facet-rich Cu (SF-Cu) catalyst to result in a lifetime of over 1000 hours.
- MEA membrane-electrode assembly
- ECO 2 R has wide variety of applications, for example, formation of high-value chemicals and feedstocks using renewable electricity, which could decouple the chemical and fuel productions from fossil fuels and thus close the carbon loop, offering possibilities to mitigate greenhouse gas emissions.
- Optimizing selectivity, i.e., Faradaic efficiency (FE), of catalysts for high-value products such as CO, HCOOH, and C 2 H 4 , increasing their productivity (current density), and lowering overpotentials of the reduction reactions have become priorities and been with some significant advances.
- FE Faradaic efficiency
- one of the problems is the system stability. Formation and crossover of carbonate in both alkaline and neutral electrolytes during electrolysis result in additional energy consumption and CO 2 losses, lowering the durability of ECO 2 R.
- the present disclosure provides a pure-H 2 O-fed MEA electrolysis system on a high-performance step-facet-rich Cu (SF-Cu) catalyst with fast kinetics for ECO 2 R-to-C 2 H 4 .
- the system integrates the AEM and proton exchange membrane (PEM) to selectively transport the electrogenerated OH ⁇ and H + , respectively.
- the system does not only boost the pure-H 2 O-fed ECO 2 R reaction activity by increasing the local pH on the cathode catalyst surface but also eliminates carbonate formation and crossover, leading to prolonged stability.
- An aspect of the present invention provides a pure-H 2 O-fed membrane-electrode assembly electrolysis system for electrocatalytic CO 2 reduction to ethylene and C 2+ compounds including ethanol, propanol, and acetic acid under an industrial applicable continuous flow condition with at least 1000-hour lifetime, where the system includes one or more membrane-electrode assemblies, and each of the membrane-electrode assemblies include:
- the cathode is selected from a gas diffusion electrode deposited with at least a layer of the step-facet-rich copper catalyst.
- the cathode is a carbon paper with a microporous carbon gas diffusion layer coated with the step-facet-rich copper catalyst.
- the anode is selected from titanium fiber felt supported by one or more of platinum, iridium, ruthenium, and palladium, and any oxide or alloy thereof.
- the anode is a titanium fiber felt sputtered by platinum thereon.
- the anode can be a titanium fiber felt sputtered by iridium, ruthenium, and palladium, and any oxide or alloy thereof.
- the anode can be a carbon paper supported by the one or more of platinum, iridium, ruthenium, and palladium, and any oxide or alloy thereof.
- the electrocatalytic CO 2 reduction is conducted at a temperature of about 60° C. or lower but above room temperature.
- the electrocatalytic CO 2 reduction is conducted at about 60° C.
- the alkaline anion exchange membrane is an anion exchange membrane made of N-methylimidazolium-functionalized styrene polymer.
- the alkaline anion exchange membrane is an anion exchange membrane made of N-methylimidazolium-functionalized styrene polymer with a thickness of about 0.002 inches.
- the acidic proton exchange membrane is a proton exchange membrane made of tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer.
- the acidic proton exchange membrane is a proton exchange membrane made of tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer with a thickness of about 0.007 inches and an equivalent weight of about 1100 g/mol.
- the step-facet-rich copper catalyst has a variable surface atom coordination number from 4 to 9 at either one or both of Cu (111) and Cu (100) exposed facets.
- the step-facet-rich copper catalyst has a variable surface tensile strain within 10% of an initial tensile strain thereof measured at room temperature.
- At least six of the membrane-electrode assemblies are stacked together.
- up to about 50% of Faradaic efficiency towards ethylene with a carbon dioxide-to-ethylene conversion efficiency of about 39% is achieved when a total current of 10 A is supplied across the at least six membrane-electrode assemblies through two conductive substrates sandwiching the stack of the at least six membrane-electrode assemblies with a total geometrical area of 30 cm 2 .
- the total geometrical area of the one or more of the membrane-electrode assemblies is variable subject to the demand for CO 2 reduction, current density, size of the electrolysis cell, conductivity of the electrodes, membranes and substrates thereof, etc.
- the electrolysis cell includes a stack of multiple membrane-electrode assemblies or a single membrane-electrode assembly with a relatively larger geometrical area, or both.
- the stack of multiple membrane-electrode assemblies is selected over the single membrane-electrode assembly in an industrial applicable continuous flow condition since the stack configuration is relatively more flexible and easier to be scaled up or down according to the demand for CO 2 reduction and compatibility to other equipment in an industrial plant or setting.
- Another aspect of the present invention provides a method for fabricating a pure-H 2 O-fed membrane-electrode assembly electrolysis system for electrocatalytic CO 2 reduction to ethylene and C 2 ⁇ compounds including ethanol, propanol, and acetic acid with at least 1000-hour lifetime, where the method includes:
- the step-facet-rich copper catalyst is provided by:
- At about 1:2 weight ratio of copper chloride to octadecylamine are dissolved in squalene.
- about 20:1 volume ratio of oleylamine to trioctylphosphine are mixed under heating at 200° C. under argon gas.
- the organic solution for washing the centrifuged, cooled reaction mixture is n-hexane.
- the cathode is formed with the step-facet-rich copper catalyst coated thereon by:
- the anode is formed from a titanium fiber felt supported by the anode forming mixture comprising one or more of platinum, iridium, ruthenium, and palladium, and any oxide or alloy thereof.
- the alkaline anion exchange membrane is selected from an anion exchange membrane made of N-methylimidazolium-functionalized styrene polymer with a thickness of about 0.002 inches;
- the acidic proton exchange membrane is selected from a proton exchange membrane made of tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer with a thickness of about 0.007 inches and equivalent weight of 1100 g/mol.
- At least six of the membrane-electrode assemblies are stacked with each other and sandwiched between the two conductive substrates; the electrolyte temperature is maintained at about 60° C.
- the at least six of the membrane-electrode assemblies have a total geometrical area of about 30 cm 2 .
- FIG. 1 A shows a comparison of the stability of ECO 2 R-to-C 2 H 4 on Cu-based catalysts in the flow cell or MEA cell according to certain embodiments of the present invention with that of conventional systems according to certain literatures;
- FIG. 1 B shows a result of a long-stability performance test on ECO 2 R-to-C 2 H 4 on SF-Cu in a pure-H 2 O-fed MEA-cell stack containing 6 MEA cells at a constant current of 10 A according to certain embodiments of the present invention, where the total cathode electrode area is set to be 30 cm 2 and the reaction temperature is set to be 60° C.;
- FIG. 2 A shows an SEM image of the SF-Cu catalyst according to certain embodiments of the present invention
- FIG. 2 B shows a HRTEM image of the SF-Cu according to certain embodiments of the present invention, revealing abundant stacking faults (yellow rectangular box marked with D);
- FIG. 2 C shows a HRTEM image of the SF-Cu in certain embodiments of the present invention, revealing interlaced grain (twin) boundaries (yellow rectangular box marked with E);
- FIG. 2 D shows an atomic-resolution HAADF-STEM image of stacking faults from the selected area marked with D in the rectangular box as shown in FIG. 2 B ; yellow lines highlight stacking faults;
- FIG. 2 E shows an atomic-resolution HAADF-STEM image of twin boundaries from the selected area marked with E in the rectangular box as shown in FIG. 2 C ; yellow lines highlight five-fold twin boundaries;
- FIG. 2 F shows an atomic-resolution HAADF-STEM image of surface step-facets of the SF-Cu induced by a stacking fault and a twin boundary, where both the stacking fault and twin boundary along ⁇ 111 ⁇ planes are indicated by white dashed lines;
- FIG. 2 G shows geometric-phase analysis (GPA) strain mapping of tensile strain (C) near the surface exits of the stacking fault and the twin boundary as shown in FIG. 2 F using the lattice far from defects as a reference (zero strain), where the tensile strain as measured is perpendicular to the ⁇ 111 ⁇ plane along which the stacking fault and twin boundary align with each other;
- GPA geometric-phase analysis
- FIG. 3 shows in-situ heating characterization on different states of SF-Cu: (A and B) TEM images of the pristine SF-Cu (Before) and the SF-Cu heated at 650° C. for 20 min (After); (C and D) HRTEM images of the pristine SF-Cu (Before) and the SF-Cu heated at 650° C. for 20 min (After);
- FIG. 4 shows SEM images and size distribution of different catalyst nanoparticles: (A-C) SF-Cu; (D-F) Cu-250; (G-I) Cu-350; (J-L) Cu-450;
- XANES X-ray absorption near edge structure
- FIG. 6 A schematically depicts reaction scheme of ECO 2 R in the pure-H 2 O-fed MEA cell assembled with AEM and PEM according to certain embodiments of the present invention
- FIG. 6 B shows FEs toward ECO 2 R products under a range of applied current densities in the MEA cell with pure H 2 O as the electrolyte, and the corresponding cell voltages without iR compensation; Pt/Ti is used as the anode electrode and the reaction temperature is set at 60° C.;
- FIG. 6 C schematically depicts the MEA-cell stack containing 6 MEA cells for ECO 2 R reaction according to certain embodiments of the present invention
- FIG. 6 D shows stability monitoring of the MEA-cell stack containing 6 MEA cells at a constant current of 10 A according to certain embodiments of the present invention, where an inset shows a digital photograph of the monitoring system;
- FIG. 7 shows an X-ray diffraction (XRD) patterns of SF-Cu, Cu-250, Cu-350 and Cu-450 on the carbon paper, and bare carbon paper;
- FIG. 8 shows an X-ray photoelectron spectroscopy (XPS) spectra of SF-Cu, Cu-250, Cu-350 and Cu-450:
- XPS X-ray photoelectron spectroscopy
- FIG. 9 shows an X-ray absorption spectroscopy (XAS) spectra of SF-Cu, Cu-250, Cu-350 and Cu-450, and the standard Cu foil, CuO and Cu 2 O references: (A) Cu K-edge XANES spectra; (B) Fourier transform of Cu K-edge extended X-ray absorption fine structure (EXAFS) spectra;
- XAS X-ray absorption spectroscopy
- FIG. 10 shows Cu K-edge EXAFS fitting curves at R and q space, respectively: (A1-A2) Cu foil reference; (B1-B2) SF-Cu; (C1-C2) Cu-250; (D1-D2) Cu-350; (E1-E2) Cu-450;
- FIG. 11 shows two-dimensional plots of wavelet transform EXAFS (2D WT EXAFS): (A) Standard Cu foil reference; (B) SF-Cu; (C) Cu-250; (D) Cu-350; (E) Cu-450; (F) Standard Cu 2 O reference; (G) Standard CuO reference;
- FIG. 12 shows exposed facets of SF-Cu determined by lead underpotential deposition (Pd-UPD);
- FIG. 13 shows atomic models with different CNs on Cu (111) (side view, top view and Cu site with the different CN):
- FIG. 14 shows atomic models with different CNs on Cu (111) (side view, top view and Cu site with the different CN): (A-F) CN: 7, 7, 6, 5, 5 and 5, respectively;
- FIG. 15 shows Atomic models with different CNs on Cu (100) (side view, top view and Cu site with the different CN): (A) The perfect Cu(100), CN: 8. (B and C) CN: 7 and 6, respectively;
- FIG. 16 shows atomic models with different CNs on Cu(100) (side view, top view and Cu site with the different CN): (A-D) CN: 6, 6, 5 and 4, respectively;
- FIG. 21 shows a comparison of the total current densities on SF-Cu, Cu-250, Cu-350 and Cu-450 for the ECO 2 R reaction in a flow cell with 1 M KOH as the electrolyte under a range of applied potentials;
- FIG. 22 shows a comparison of FEs and partial current densities toward C 2+ products on SF-Cu, Cu-250, Cu-350 and Cu-450 for the ECO 2 R reaction in a flow cell with 1 M KOH as the electrolyte under a range of applied potentials: (A) FEs toward C 2+ products; (B) Partial current densities of C 2+ ;
- FIG. 23 shows relationships between (A) strain, CN and the peak j C2H4 ; and (B) strain, CN and the j without H2 for the ECO 2 R reaction in a flow cell with 1 M KOH as the electrolyte;
- FIG. 24 shows a relationship between strain, CN and the j H2 under the peak ECO 2 R performance in a flow cell with 1 M KOH as the electrolyte;
- FIG. 25 shows SEM images (A-C) and size distribution (D) of the oxide-derived Cu nanoparticles
- FIG. 26 shows XRD patterns of SF-Cu, oxide-derived Cu on the carbon paper, and bare carbon paper;
- FIG. 27 shows XPS spectra of the oxide-derived Cu: (A) Cu 2p XPS spectrum; (B) Cu LMM Auger spectrum; (C) O 1s XPS spectrum;
- FIG. 29 shows a comparison of total current densities on SF-Cu and oxide-derived Cu for the ECO 2 R reaction in a flow cell with 1 M KOH as the electrolyte under a range of applied potentials;
- FIG. 30 shows comparisons of the ECO 2 R performance on SF-Cu and oxide-derived Cu in a flow cell with 1 M KOH as the electrolyte under a range of applied potentials: (A and C) comparisons of FEs toward C 2+ and C 2 H 4 , respectively; (B and D) comparisons of partial current densities of C 2+ and C 2 H 4 , respectively;
- FIG. 31 shows ECO 2 R performance on SF-Cu and SF-Cu/PMMA in a flow cell with 1 M H 3 PO 4 :
- A The FE and total current density on SF-Cu under a range of applied potentials, no ECO 2 R product, just H 2 ;
- C SEM image of the surface of SF-Cu/PMMA;
- D Cross-sectional SEM image of SF-Cu/PMMA;
- FIG. 33 shows ECO 2 R performance on SF-Cu/PMMA in a flow cell with 1 M H 3 PO 4 containing 3 M KI as the catholyte and 1 M H 3 PO 4 as the anolyte: (A) FEs towards ECO 2 R products under a range of applied potentials; (B) corresponding total current density under a range of applied potentials;
- FIG. 34 shows a digital photograph of the flow channel after the ECO 2 R reaction on SF-Cu for ⁇ 10 min in an MEA cell with 1 M H 3 PO 4 containing 3 M KNO 3 as the anolyte;
- FIG. 35 shows ECO 2 R performance on SF-Cu in an MEA cell with 1 M KOH as the anolyte: (A) FEs toward ECO 2 R products under a range of applied potentials; (B) corresponding total current density under a range of applied potentials;
- FIG. 36 shows comparisons of the ECO 2 R performance on SF-Cu in an MEA cell with 1 M KOH/pure H 2 O as the anolyte under a range of applied potentials:
- A, C and E show comparisons of FEs toward C 2 H 4 , C 2+ , and all ECO 2 R products, respectively;
- B, D and F show comparisons of partial current densities of C 2 H 4 , C 2+ , and all ECO 2 R products, respectively;
- the reaction temperature of the ECO 2 R reaction under pure H 2 O is 60° C. and other ECO 2 R reactions are carried out at room temperature;
- FIG. 37 schematically depicts the MEA-cell stack containing 6 repeating MEA cells for performing the ECO 2 R reaction according to certain embodiments of the present invention
- FIG. 38 shows stability performance of ECO 2 R-to-C 2 H 4 on SF-Cu in an MEA cell with 1 M KOH as the anolyte at 3.2 V cell voltage according to certain embodiments of the present invention
- FIG. 39 shows in-situ XRD measurement on SF-Cu for the ECO 2 R reaction in 0.1 M KOH at the 4 V cell voltage for 10 h: (A) Total current density; (B) In-situ XRD patterns, corresponding to FIG. 39 A );
- FIG. 40 shows in-situ XRD measurement on SF-Cu for the ECO 2 R reaction in 0.1 M KOH at the stepped cell voltages for 8 h: (A) Total current density; (B) In-situ XRD patterns, corresponding to FIG. 40 (A) ;
- FIG. 41 shows the ECO 2 R mechanism and effects of CN and tensile strain on ECO 2 R by DFT calculations and experiments:
- A In-situ Raman spectra of ECO 2 R on SF-Cu for 1 h in a customized flow cell with a two-electrode system at 4 V cell voltage according to certain embodiments of the present invention;
- B FEs and
- C partial current densities toward C 2 H 4 on SF-Cu for ECO 2 R and ECOR reactions in 1 M KOH under a range of the applied potentials;
- D A reaction energy diagram for the ECO 2 R to C 2 H 4 on the perfect Cu and SF-Cu models via the direct *CO hydrogenation to *CHO followed by the unoccupied *CO and the *CHO dimerization pathway.
- FIG. 42 shows a reaction energy diagram for the ECO 2 R into the *CO intermediate on the perfect Cu and SF-Cu models
- FIG. 43 shows in-situ Raman measurements on SF-Cu for the ECO 2 R reaction in 0.1 M KOH at the different cell voltages
- FIG. 44 shows the total current density of the in-situ Raman measurement on SF-Cu for the ECO 2 R reaction in a flow cell with 0.1 M KOH at a cell voltage of 4 V;
- FIG. 45 shows in-situ Raman measurement on SF-Cu for the ECO 2 R reaction in a flow cell with 0.1 M KOH at a cell voltage of 6 V: (A) Total current density; (B) In-situ Raman spectra for 1 h;
- FIG. 46 shows ECOR performance and comparisons with ECO 2 R performance on SF-Cu in the flow cell with 1 M KOH as the electrolyte: (A) FEs toward ECOR products under a range of applied potentials; (B) Total current density for ECOR under a range of applied potentials; (C) Comparisons of FEs and (D) partial current densities toward C 2+ on SF-Cu for ECO 2 R and ECOR in 1 M KOH under a range of applied potentials;
- FIG. 47 shows a comparison in reaction energy for the ECO 2 R on the perfect Cu and SF-Cu models via the direct *CO hydrogenation to *CHO followed by the unoccupied *CO and the *CHO dimerization pathway versus the direct *CO hydrogenation to *COH followed by the unoccupied *CO and the *COH dimerization pathway versus 2*CO hydrogenation to 2*CHO followed by *CHO dimerization pathway;
- FIG. 48 shows temperature-programmed desorption (TPD) of (A) CO 2 and (B) CO on SF-Cu, Cu-250, Cu-350 and Cu-450.
- the SF-Cu catalyst delivered ECO 2 R to C 2 H 4 with ⁇ 80% FE and 568 mA/cm 2 partial current density (j C2H4 ) at about ⁇ 0.58 V (versus a reversible hydrogen electrode (RHE) throughout the text, unless otherwise noted) in a flow cell.
- the impressive ECO 2 R performance of SF-Cu is explicitly linked with the manipulations of its coordination number (CN) and tensile strain ( FIGS. 5 F, 23 and 41 ).
- the ECO 2 R reaction is then carried out in a flow cell with the strong acid as the electrolyte, but the strong-acid system cannot satisfy the industrially more promising MEA-cell architecture.
- pure H 2 O is used as an electrolyte to perform ECO 2 R-to-C 2 H 4 /C 2+ compounds in an MEA cell assembled with AEM and PEM.
- the SF-Cu catalyst reduces CO 2 to C 2 H 4 with ⁇ 42% FE and 300 mA/cm 2 total current density at ⁇ 4.3 V cell voltage without iR compensation.
- the ECO 2 R is scaled up in a pure-H 2 O-fed 6-MEA-cell stack.
- FIGS. 2 A- 2 E the SF-Cu nanoparticles with an average diameter of ⁇ 60 nm ( FIG. 2 A ) are first prepared. Detailed preparation methods of the SF-Cu nanoparticles can be found in some of the examples described hereinafter.
- the high-resolution transmission electron microscopy (HRTEM) and aberration-corrected high-angle-annular-dark-filed scanning TEM (HAADF-STEM) images of the SF-Cu nanoparticles reveal abundant stacking faults that intersect with each other ( FIGS. 2 B and 2 D ).
- FIG. 2 C shows that the multitudinous interlaced grain boundaries in SF-Cu contain ⁇ 3 coincident site lattice (CSL) boundaries and form some typical five-fold twinning structures (being twin boundaries as highlighted by yellow lines in HAADF-STEM image shown in FIG. 2 E ), which can induce the intrinsic stress, especially large tensile strain/stress on the surface layer.
- the GPA map shown in FIG. 2 G reveals the local tensile strain as large as ⁇ 0.8% around the surface exits of both twin boundaries and stacking faults.
- the stepped facets are induced at the surface exits of twin boundaries and stacking faults, giving rise to surface Cu atoms with reduced CNs.
- both the high surface tensile strain and low CNs can lead to the high-energy active surfaces for catalytic reactions, it suggests that the abundant stacking faults and grain boundaries in SF-Cu induce the extraordinary ECO 2 R performance in the present invention.
- SF-Cu is annealed at various elevated temperatures (250, 350 and 450° C.; Cu-250, Cu-350 and Cu-450) to alter their microstructures.
- the high-temperature treatment will induce rearranging atoms to reach a more thermodynamically favorable state in minimizing the total surface energy.
- the effect of annealing on the SF-Cu in the present invention has been explicitly shown by in-situ heating TEM images, which demonstrate a decrease or even a disappearance of stacking faults and twin boundaries in the SF-Cu at high temperatures ( FIG. 3 ). After each high-temperature treatment, there is no appreciable change in sample size distributions ( FIG.
- the lead underpotential deposition (Pb UPD) is used to identify the exposed facets of SF-Cu, which are Cu (111) and Cu (100) ( FIG. 12 ). Then, the atomic structure simulations are carried out to show the possible CNs of Cu atoms on the exposed facets (111 and 100) of SF-Cu ( FIGS. 13 - 16 ).
- the perfect Cu (111) plane is composed of the surface atoms with a CN of 9 ( FIG. 13 A ), while other CNs (8, 7, 6 and 5) are also possible, depending on different sliding ways ( FIGS. 13 B-D and 14 A-F).
- the perfect Cu (100) plane contains surface atoms with a CN of 8 ( FIG. 15 A ) and atomic sites with lower CNs include 7, 6, 5 and 4 ( FIGS. 15 B-C and 16 A-D).
- CNs of Cu atoms on the SF-Cu surface vary from 9 to 4 due to abundant stacking faults and interlaced grain boundaries.
- SF-Cu shows the best ECO 2 R performance and the highest FEs toward C 2 H 4 and C 2+ in the flow cell among all the samples under 1 M KOH electrolyte condition ( FIGS. 5 C and 17 - 20 ).
- the peak. FE toward C 2 H 4 is up to ⁇ 80% at about ⁇ 0.58 V, at which j C2H4 reaches ⁇ 568 mA/cm 2 .
- the half-cell energy efficiency (EE half-cell ) of C 2 H 4 is up to ⁇ 51.0, With an increase in treatment temperature, the samples show a noticeable decline for ECO 2 R activity ( FIG. 21 ).
- an oxide-derived Cu based on SF-Cu is prepared and characterized ( FIGS. 25 - 27 ).
- the oxide-derived Cu barely show any improvement in ECO 2 R performance in terms of either FEs or current densities ( FIGS. 28 - 30 ), which suggests that oxide-derived Cu (or the oxidation state thereof) is not a crucial factor that determines the ECO 2 R performance in the present invention, as opposed to some previous findings.
- SF-Cu GDE is directly used as the cathode to perform ECO 2 R in a flow cell with 1 M H 3 PO 4 as the electrolyte. No ECO 2 R product is observed, except H 2 ( FIG. 31 (A) .
- a buffer layer is assembled on the SF-Cu GDE to slow the out diffusion of OH ⁇ and K + from SF-Cu surface, in order to enrich potassium ion concentration and increase local pH on said surface ( FIGS. 31 C and 31 D ).
- the buffer layer can be a cross-linked microporous polymethyl methacrylate (PMMA) layer and assembled on the SF-Cu GDE (SF-Cu/PMMA).
- the C 2+ FE is improved to ⁇ 48% ( ⁇ 33% toward C 2 H 4 , ⁇ 14% toward C 2 H 5 OH and ⁇ 1% CH 3 COOH) ( FIG. 33 A ) with a total current density of ⁇ 345 mA/cm 2 at ⁇ 1.1 V ( FIG. 33 B ).
- the present SF-Cu catalyst shows higher FEs toward C 2 H 4 and C 2+ for ECO 2 R than any conventional acidic system such as that disclosed in Huang et al. (2021) (Table 2), due to an improved catalyst structure and morphology in the present SF-Cu catalyst.
- an industrially more applicable MEA cell is initially assembled with Nafion membrane in acidic media to perform the ECO 2 R reaction.
- 1 M H 3 PO 4 containing 3 M KNO 3 is used as the anolyte.
- K + and H + /H 3 O + in the anolyte would pass through the Nafion membrane to the SF-Cu surface under the electric field.
- K + would promote ECO 2 R while H + /H 3 O + would serve as the proton source.
- some ECO 2 R products such as CO and C 2 H 4 are formed during this initial testing, the ECO 2 R reaction is shut down after a few minutes, and hydrogen evolution reaction (HER) became dominant.
- H 2 O as the proton source will participate in the ECO 2 R reaction at the cathode, and it will be oxidized into O 2 at the anode ( FIG. 6 C ).
- the remaining OH ⁇ at the cathode and H + at the anode will transport through AEM and PEM, respectively, forming H 2 O at the interface of AEM and PEM (Eq. 3-5), which can effectively increase the local pH on the surface of the cathode catalyst.
- a small amount of CO 2 can dissolve in pure H 2 O to form H 2 CO 3 (Eq. 6), the alkaline AEM and acidic PEM will effectively suppress H 2 CO 3 formation and shift the equilibrium reaction to the left.
- the flow rate of the CO 2 inlet will be about 30 sccm.
- all ECO 2 R reactions are conducted at a reaction temperature of about 60° C., and Ti fiber felt sputtered by Pt (Pt/Ti) is selected as the anode electrode.
- Sustainion X37-50 is selected as AEM
- Nafion 117 is selected as PEM for electrogenerated OH ⁇ and H + ion exchange membranes, respectively.
- bipolar membrane can be used as the AEM/PEM.
- Sustainion X37-50 and Nafion 117 are respectively selected as AEM and PEM over bipolar membrane in assembling the present MEA cell system.
- the present MEA cell system includes a cathode selected from SF-Cu GDE and an anode selected from Ti fiber felt sputtered by Pt (Pt/Ti), where between the cathode and anode there is a combination of the AEM and PEM separating the cathode from the anode such that the cathode is in contact with the AEM while the anode is in contact with the PEM.
- the ECO 2 R reaction on the SF-Cu in the present MEA cell is carried out at a temperature not to suppress ECO 2 R and make HER dominant under a galvanostatic mode.
- the temperature sufficient to induce ECO 2 R and not to make HER dominant under the galvanostatic mode is about 60° C. ( FIG. 6 B ).
- the ECO 2 R selectivity reaches the peak up to ⁇ 66% FE, including ⁇ 52% FE toward C 2+ (C 2 H 4 FE of ⁇ 43%, C 2 H 5 OH FE of ⁇ 6%, CH 3 CH 2 CH 2 OH FE of 2% and CH 3 COOH FE of ⁇ 1%).
- the cell voltage is ⁇ 4.3 V without iR compensation. Without counting the energy consumed by the reaction temperature, the proposed pure-H 2 O-fed MEA-cell architecture delivers a full-cell energy efficiency (EE full-cell ) of ⁇ 18.2%.
- the product analysis shows that the peak FEs and partial current densities of ECO 2 R products in the proposed pure-H 2 O-fed MEA system are even comparable to those in the MEA cell with 1 M KOH ( FIGS. 35 and 36 ).
- the pure-H 2 O-fed MEA cell can circumvent the theoretical-CO 2 -utilization limit for the ECO 2 R reaction by thoroughly eliminating the carbonate formation and crossover.
- an MEA-cell stack system containing 6 MEA cells ( FIGS. 6 C and 37 ) is assembled and tested to evaluate its durability and practicality.
- a total current of 10 A six sets of SF-Cu GDEs with a total geometrical area of 30 cm 2 deliver a FE of ⁇ 50% toward C 2 H 4 ( FIG. 1 B ).
- the 6-MEA cell stack system can remain stable for more than 1000 hours with a full-cell-stack voltage between 25 and 27 V without iR compensation ( ⁇ 4.4 V cell voltage for each set of the 6 MEA cells as shown in FIG. 6 D ).
- the stability of ECO 2 R on SF-Cu in an MEA cell with the alkaline condition is even less than 4 h ( FIG. 38 ).
- the 6-MEA cell stack system can deliver up to ⁇ 39% CO 2 -to-C 2 H 4 conversion, and no GDE flooding is observed after 1000-h operation. This significant difference in performance might be due to an elevated reaction temperature ( ⁇ 60° C.) which allows a small amount of accumulated H 2 O on the GDEs to be discharged more quickly along with the steam.
- the pure-H 2 O-fed MEA-cell stack system is further incorporated with an integrated circuit for monitoring ECO 2 R reaction, e.g., iOS development, an inset in FIG. 6 D .
- ECO 2 R reaction e.g., ECO 2 R reaction
- FIG. 6 D Each cell in the system shows an almost identical voltage throughout the 1000-h measurement, except for some fluctuations at the first 100 h, demonstrating the possibility of the MEA-cell stack for the stable ECO 2 R at the industrial level.
- FIGS. 41 - 48 outstanding ECO 2 R to C 2 H 4 performances of SF-Cu and ECO 2 R reaction pathway are demonstrated by density functional theory (DFT) calculations and in-situ and ex-situ measurements, where the SF-Cu in the pure H 2 O system is shown to attribute to the combination of this new electrolysis architecture with a superior catalytic activity due to the low CN and high tensile strain of the SF-Cu.
- DFT density functional theory
- DFT calculations are performed on the perfect Cu (111) and SF-Cu (111) models to reveal the outstanding ECO 2 R to C 2 H 4 performance of SF-Cu.
- the unit cell of the SF-Cu model is expanded with a factor of 1.1, meaning 10% tensile strain, and CN of the SF-Cu model is set to 7.
- the reaction energy of CO 2 -to-*COOH at the SF-Cu surface is 0.39 eV ( FIG. 42 ), much lower than that of the perfect Cu (0.75 eV).
- the *COOH could be easily converted into *CO due to the negative reaction energies for the perfect Cu and SF-Cu model.
- the *CO intermediate for the ECO 2 R on SF-Cu is observed by in-situ Raman measurements at different potentials ( FIGS. 41 A and 43 - 45 ).
- the peaks located in the range of 270-360 cm ⁇ 1 are related to the Cu—CO frustrated rotation and Cu—CO stretch.
- the peaks at the 1900-2200 cm ⁇ 1 can be ascribed to the C ⁇ O stretch of the surface-absorbed CO, including atop-bound CO and bridge-bound CO.
- the vibration of C—H is also observed in the region from 2700 to 3000 cm ⁇ 1 , which can be derived from hydrogenated intermediates (such as *CHO, *COCHO, etc.).
- a more precise assignment of these peaks is highly challenging due to the complexity of hydrogenated intermediates of ECO 2 R.
- SF-Cu shows a lower j C2H4 /j C2+ for the direct ECOR ( FIGS. 41 B, 41 C and 46 ), indicating that the *CO dimerization to *OCCO may not be the main C—C coupling pathway for the ECO 2 R on SF-Cu.
- two hydrogenation paths of *CO (*CO-to-*CHO and *CO-to-*COH) are calculated ( FIG. 47 ).
- the *CO-to-*CHO hydrogenation has less reaction energy than that of *CO-to-*COH.
- FIG. 41 D shows that SF-Cu decreases the reaction energy of *CO-to-*CHO hydrogenation from 0.56 to 0.30 eV ( FIG. 41 D ).
- thermodynamic and kinetic advantages are ascribed to the effects of the low CN and high tensile strain of SF-Cu.
- FE up to 50% towards C 2 H 4 is achieved with CO 2 -to-C 2 H 4 conversion of ⁇ 39% at a total current of 10 A, with a system stability in terms of constant output over 1000 h.
- selectivity of products can be improved and operating voltage thereof may be decreased. It is believed that pure-H 2 O-fed ECO 2 R-to-C 2 H 4 in the proposed MEA architecture injects new vitality into the ECO 2 R technology.
- Potassium hydroxide (KOH, >85.0%), Nickel foam (2 mm thickness, 99.9%), and Titanium fiber felt (0.25 mm thickness, 99.9%) were purchased from Sinopharm Chemical Reagent Co., Ltd. (China).
- Isopropanol C 3 H 8 O, IPA, >99.5%, 3776
- the anion exchange membrane (Fumasep FAA-3-PK-75), gas diffusion layer (carbon paper, GDE, Sigracet 39 BB), and Nafion® 117 membrane (591239) were purchased from FuelCellStore.
- the alkaline ionomer solution (5% in ethanol, Sustainion XA-9) and anion exchange membrane (Sustainion X37-50) were purchased from Dioxide Materials.
- the SF-Cu samples were annealed at various temperatures (250, 350, and 450° C.; Cu-250, Cu-350, and Cu-450) in the tube furnace for 2 h under a mixed gas (H 2 /Ar: 5 v/v %; 200 seem (standard cubic centimeters per minute)) to prevent oxidization.
- the oxide-derived Cu was prepared by directly calcining SF-Cu at 450° C. in the air for 2 h.
- Cathode GDEs were prepared on conventional carbon paper.
- the catalyst was dispersed in a mixed solution containing H 2 O, IPA (1:4 v/v) and some alkaline ionomer solution (5 wt. % vs. catalyst, Sustainion XA-9) by the sonication for 1 h to form a 1 mg/mL catalyst ink.
- GDEs were fabricated by spraying the ink onto the carbon paper with a microporous carbon gas diffusion layer with the loading of ⁇ 1 mg/cm 2 , followed by drying at 120° C. in a vacuum for 1 h before use (SF-Cu GDE).
- Anode electrode was the mixture of IrO x and RuO x supported carbon paper.
- the SF-Cu GDE and Pt/Ti GDE were directly used as the cathode and anode electrodes, respectively.
- Electrochemical tests in the flow cell and MEA cell were performed using an electrochemical workstation (CHI 660E) connected to a current booster (CHI 680C), except for the MEA-cell stack.
- the mass flow controller (MFC, Alicate Scientific MC) was used to control the CO 2 flow rate.
- the flow rate of the electrolyte stream was 5 mL/min controlled by a peristaltic pump unless otherwise noted.
- the area of the cathode in the flow cell and MEA was 1 cm ⁇ 1 cm unless otherwise noted. All ECO 2 R measurements were carried out at room temperature unless otherwise noted.
- the Hg/Hg 2 Cl 2 SCE, saturated KCl
- EIS electrochemical impedance spectroscopy
- GC gas chromatograph
- NMR nuclear magnetic resonance
- ECZ500R 500 MHz, JEOL
- GC was equipped with two thermal conductivity detectors (TCD) for H 2 , O 2 , N 2 , He, CO and CO 2 signals and a flame ionization detector (FID) for CH 4 , C 2 H 4 and C 2 H 6 signals.
- GC was composed of packed columns of two Porapak-N, a Molecular sieve-13X, a Molecular sieve-5A, a Porapak-Q and an HP-PLOT AL/S column, and employed He (99.999%) and N 2 (99.999%) as the carrier gases.
- He used as the internal standard was fed at 10 seem and mixed with the outlet gas stream of the cell before injecting to GC (20).
- the FEs of gas products were calculated by the following equation:
- FE ⁇ ( % ) N x ⁇ F ⁇ m x ⁇ f C ⁇ O 2 j total ⁇ 100 ⁇ %
- N x is the number of electrons transferred for the specific product (x)
- F is the Faradaic constant
- m x is the molar fraction of the specific product (x) determined by GC
- f CO2 is the molar flow rate of the CO 2
- j total is the total current density.
- liquid products were analyzed by 500 M Hz 1 H NMR spectroscopy (ECZ500R, JEOL) with water suppression. TSP and D 2 O were used as the reference standard and lock solvent, respectively.
- the FEs of liquid products were calculated by the following equation:
- N x is the number of electrons transferred for the specific liquid product (x)
- F is the Faradaic constant
- C x is the concentration of the specific liquid product (x) determined by 1 H NMR
- V x is the volume of the electrolyte
- Q total is the total charge.
- E OER ⁇ and E x ⁇ are the thermodynamic potentials (vs. RHE) for OER and the electrocatalytic CO 2 reduction to the product (x), respectively, FE x is the FE of the product (x), E C is the applied potentials at the cathode, and E Full-cell is the cell voltage of the MEA system.
- In-situ Raman measurements were carried out by a customized spectro-electrochemical flow cell fabricated with a sapphire window (the thickness of 0.15 ⁇ 0.02 mm) in front of the cathode GDE.
- the Ni felt was used as a counter electrode.
- the overall system was operated in a two-electrode setup.
- the electrolyte (0.1 M KOH) was pumped into a sapphire window at a constant flow rate of 5 mL/min by a peristaltic pump over the cathode GDE, and the thickness of the electrolyte level on the cathode surface was 1.5 mm.
- CO 2 was supplied to the back of the cathode GDE through the serpentine flow channel to guide the CO 2 at a flow rate of 30 seem controlled by an MFC (Alicate Scientific MC).
- Raman spectra were collected under the accumulation time of 4 s and accumulation number of 10 times by using a WITEC Confocal Raman microscope with an objective (50 ⁇ ) and a 633 nm laser. The cell voltage was applied in potentiostatic mode and recorded without iR compensation.
- the customized spectro-electrochemical flow cell was employed to perform the in-situ XRD measurements operated in a two-electrode setup. Ni felt was used as a counter electrode, 0.1 M KOH was used as the electrolyte, and the CO 2 (30 sccm) was supplied to the back of the cathode GDE.
- the single test time was about ⁇ 8 min in the range (2 ⁇ ) of 300 to 85°.
- the cell voltage was applied in potentiostatic mode and recorded without iR compensation.
- Pb underpotential deposition Pb underpotential deposition
- Pb-UPD measurements were conducted in a three-electrode single-compartment cell.
- a graphite carbon rod and Ag/AgCl (3 M KCl) were used as the counter electrode and reference electrode, respectively.
- An L-type glassy-carbon electrode loaded the sample with a diameter of 3 mm was employed as the working electrode.
- An N 2 -purged 0.1 M KNO 3 with 1 mM Pb(NO 3 ) 2 was added with HNO 3 to adjust the pH to 1, used as the electrolyte.
- Cyclic voltammetry (CV) with a sweep rate of 100 mV/s was used for measurements.
- Temperature-programmed desorption (TPD) measurements of CO 2 on samples were conducted with an adsorption/desorption system.
- 1 cm 2 GDE with the catalyst load of ⁇ 1 mg/cm 2 was ground into powder, the powder was placed in a U-shaped quartz microreactor.
- the outlet of the U-shaped quartz microreactor was connected to GC (GC-2014, Shimadzu) with a TCD detector.
- the CO 2 (40 sccm) was injected into the U-shaped quartz microreactor and kept flowing for 60 min, followed by flushing the sample using the He stream (40 sccm) until obtaining a stable baseline of GC.
- TPD measurements were then conducted from room temperature to 800/500° C. at a ramp rate of 10° C./min, and GC would detect the desorbed CO 2 from the sample surface.
- the unit cell was expanded with a factor of 1.1 and then fully relaxed until getting convergence.
- the lattice constant was determined to be 4.000 ⁇ .
- Six-layer p(4 ⁇ 4) supercells of Cu (111) facet were used, with the lower three layers fixed.
- the vacuum thickness in a direction perpendicular to the plane of the catalyst was at least 15 ⁇ to avoid the attractions from adjacent periodic mirror images. At all intermediate states, two water molecules are added near the slab surface to take the effect of solvation into account.
- E(H) is half of the H 2 (g) energy under 1.013 bar at 298.15K
- E(H 2 O) is the energy of H 2 O (g) under 0.035 bar at 298.15 K
- E(OH) E(H 2 O) ⁇ E(H).
- the zero-point energy and entropy were corrected by calculating the vibrational frequencies through density functional perturbation theory at 298.15 K.
- TEM images were collected on a JEOL JEM-2100F at 200 kV.
- Aberration-corrected HAADF-STEM images were collected on a TFS Spectra 300 at 300 kV.
- GPA analysis on atomic-resolution images was performed using Digital Micrograph software to derive the lattice strain. Only strain perpendicular to the stacking faults and twin boundaries was measured, using the lattice far from these defects as a reference (zero strain).
- SEM images were taken on the field emission Tescan MAIA3.
- XPS spectra were collected on a Thermo Scientific Nexsa X-ray photoelectron spectroscopy using Al K ⁇ radiation, and C is (284.6 eV) as a reference.
- the hard X-ray absorption spectroscopy measurements were conducted at the beamline BL01C of the Synchrotron Radiation Research Center (SRRC) in Hsinchu (Taiwan).
- SRRC Synchrotron Radiation Research Center
- the present invention provides a stackable MEA electrolysis cell system that can be operable with pure H 2 O such that carbonate formation and crossover can be eliminated. It is easy to be fabricated and scaled up or down according to industrial application and CO 2 reduction demand.
- the present invention is not just cost-efficient but also a more environmental-friendly way to reduce CO 2 . Higher yield of useful by-products from ECO 2 R reaction generated by the present invention is also resulted.
Abstract
Description
Cathode: 2CO2+8H2O+12e −→C2H4+12OH− (1)
12OH−+6CO2→6CO3 2−+6H2O (2).
-
- an anode;
- a cathode;
- an anion exchange membrane;
- a proton exchange membrane;
- a step-facet-rich copper catalyst disposed at the cathode; and
- an electrolyte,
- where:
- the cathode is arranged in contact with the anion exchange membrane;
- the anode is arranged in contact with the proton exchange membrane;
- the anion exchange membrane and proton exchange membrane are arranged in contact with each other;
- the electrolyte is selected from pure H2O as proton source for the electrocatalytic CO2 reduction at the cathode under a forward bias mode of the system;
- the anion exchange membrane is selected from alkaline anion exchange membrane or bipolar membrane; and
- the proton exchange membrane is selected from acidic proton exchange membrane or bipolar membrane.
-
- providing a step-facet-rich copper catalyst;
- preparing a step-facet-rich copper catalyst-containing ink composition for forming a cathode with the step-facet-rich copper catalyst thereon;
- forming the cathode with the step-facet-rich copper catalyst thereon;
- preparing an anode-forming mixture for forming an anode;
- forming the anode from the anode-forming mixture supporting an anode material; providing an alkaline anion exchange membrane and an acidic proton exchange membrane between said cathode and anode, where the alkaline anion exchange membrane is arranged in contact with the cathode; the acidic proton exchange membrane is arranged in contact with the anode; and the alkaline exchange membrane and acidic proton exchange membrane are in contact with each other, thereby forming a multi-layered structure of the membrane-electrode assembly;
- sandwiching one or more of the membrane-electrode assemblies with two conductive substrates;
- feeding pure H2O as an electrolyte into a container containing the one or more of the membrane-electrode assemblies being sandwiched between the conductive substrate; providing a power supply to the one or more of the membrane-electrode assemblies through the two conductive substrates;
- maintaining the electrolyte at a temperature sufficient for the electrocatalytic CO2 reduction to ethylene to last for at least 1000 hours with no dominant hydrogen evolution reaction.
-
- dissolving copper chloride and octadecylamine into squalene at about 80° C. under an argon atmosphere for about 0.5 hours until a copper-based stock solution is formed;
- mixing oleylamine and trioctylphosphine under heating the mixture to about 200° C. at the argon atmosphere with vigorous agitation to form a mixture;
- injecting the copper-based stock solution into the mixture at about 200° C. and maintained for about 5 hours to form a reaction mixture;
- cooling the reaction mixture naturally, centrifuging the cooled reaction mixture, followed by washing with an organic solution for a few times; and
- removing supernatant after said washing and blow drying pellet with argon gas under room temperature to obtain the step-facet-rich copper catalyst in solid form.
-
- dispersing the solid step-facet-rich copper catalyst into a mixed solution containing water, isopropyl alcohol and an alkaline ionomer solution;
- mixing the solid step-facet-rich copper catalyst with the mixed solution by sonication for about an hour until the step-facet-rich copper catalyst-containing ink composition is formed;
- coating the step-facet-rich copper catalyst-containing ink composition onto a carbon paper with a microporous carbon gas diffusion layer;
- drying the coated step-facet-rich copper catalyst-containing ink composition on the carbon paper in vacuum for about an hour.
TABLE 1 | ||||||||
D-W | R- | |||||||
factor | Enot, | factor, | Strain, | |||||
Sample | Path | CN | R, Å | ΔR, Å | (62) | eV | % | % |
SF-Cu | Cu—Cu | 7.6 ± | 2.551 ± | 0.026 ± | 0.009 ± | 6.2 ± | 1.4 | 1.03 |
0.5 | 0.004 | 0.002 | 0.001 | 0.8 | ||||
Cu-250 | 9.8 ± | 2.540 ± | 0.021 ± | 0.009 ± | 3.8 ± | 1.7 | 0.59 | |
0.4 | 0.003 | 0.003 | 0.001 | 0.5 | ||||
Cu-350 | 9.6 ± | 2.535 ± | 0.016 ± | 0.009 ± | 3.3 ± | 1.3 | 0.40 | |
0.9 | 0.003 | 0.003 | 0.001 | 0.4 | ||||
Cu-450 | 9.9 ± | 2.532 ± | 0.004 ± | 0.008 ± | 2.7 ± | 1.2 | 0.28 | |
0.8 | 0.002 | 0.004 | 0.001 | 0.4 | ||||
|
12 | 2.525 ± | — | 0.007 ± | 2.1 ± | 1.8 | — | |
0.005 | 0.001 | 0.5 | ||||||
CN: coordination number; R: bond length; o: Debye-Waller factor. |
TABLE 2 | ||||||||
Total C2+ | ||||||||
Potential | C2H4 | Product | ||||||
(V vs. | jC2H4 | Faradaic | jC2+ | Faradaic | Stability | |||
Catalyst | Electrolyte | RHE) | (mA/cm2) | Efficiency | (mA/cm2) | Efficiency | (h) | Ref. |
SF-Cu | 1M | ~−0.58 | ~569 | ~80% | ~607 | ~85.48% | <1 | — |
in the flow | KOH | |||||||
cell | 1M | ~−1.1 | ~114 | ~33% | ~167 | ~48.57% | <4 | |
(Present | H3PO4 + | |||||||
Invention) | 3 M KI// | |||||||
1M | ||||||||
H3PO4 | ||||||||
1M | ~−1.2 | ~101 | ~28% | ~147 | ~40.71% | — | ||
H3PO4 + | ||||||||
3M | ||||||||
KCl//1M | ||||||||
H3PO4 | ||||||||
SF-Cu | 1M | ~3.2 | ~134 | ~40% | ~196 | ~58.85% | <4 | |
in single | KOH | Cell | ||||||
MEA cell | Voltage | |||||||
(Present | Pure | ~4.3 | ~129 | ~43% | ~155 | ~51.58% | — | |
Invention) | H2O | Cell | ||||||
Voltage | ||||||||
MEA cell | Pure | ~25 | ~167 | ~50% | — | — | >1000 | |
stack: 6 | H2O | Cell | ||||||
MEA Cells | Voltage | |||||||
(Present | ||||||||
Invention) | ||||||||
Cu2S/Cu-V | 1M | −0.93 | ~84.8 | 21.20% | ~223.2 | 55.80% | — | Zhuang |
(Cu- | KOH | et al. | ||||||
Vacancy) | (2018) | |||||||
Cu | 1M | −0.79 | ~140 | 45.60% | ~215 | 70% | 4 | Ma et al. |
nanoparticles | KOH | (2016) | ||||||
Cu-DAT | 1M | −0.6 | ~75 | 38.20% | ~137.83 | 70.20% | — | Hoang |
wires | KOH | et al. | ||||||
(2017) | ||||||||
Cu dimer | 1M | −1.07 | 262 | 45% | N/A | N/A | ~138 | Nam et al. |
distorted | KOH | (2018) | ||||||
HKUST-1 | ||||||||
Nanoporous | 1M | −0.67 | 256 | 38.60% | 411 | 62% | ~2.1 | Lv et al. |
Cu | KOH | (2018) | ||||||
CuAg wire | 1M | −0.68 | 172 | 55.20% | 265 | 85.10% | — | Hoang et al. |
Alloys | KOH | (2018) | ||||||
Cu wires | 1M | −0.6 | ~74 | 38.20% | ~137 | 70.20% | — | |
KOH | ||||||||
Ag0.14/Cu0.86 | 1M | −0.67 | 80 | ~32% | 195 | a. 78% | ~2 | Li et al. |
KOH | (2019) | |||||||
1M | −0.84 | 75 | ~25% | 210 | a. 70% | — | ||
KHCO3 | ||||||||
Graphite/ | 7M | −0.55 | 55-70 | ~70% | 60-81 | ~81% | 150 | Dinh |
CNPS/Cu/PT | KOH | et al. | ||||||
FE | (2018) | |||||||
25 nm Cu | 3.5M | −0.67 | ~473 | ~65% | ~608 | ~81% | — | |
KOH + | ||||||||
|
||||||||
25 nm Cu | 10M | −0.54 | 219 | 66% | 275 | 83% | <0.5 | |
KOH | ||||||||
Cu4O3-rich | 0.5 m | −0.59 | 126 | 42.30% | 183.9 | 61.30% | 24 | Martić´ |
catalyst | Cs2SO4// | et al. | ||||||
2.5M | (2019) | |||||||
KOH | ||||||||
Cu2O films | 1.0M | −0.74 | 122 | 67% | — | — | <0.6 | Anastasia |
KOH | dou et al. | |||||||
(2019) | ||||||||
Cu-F | 0.75M | −0.89 | 1040 | 65% | 1280 | 80% | — | Ma et al. |
KOH | (2020) | |||||||
1.0M | −0.75 | 720 | ~60% | 996 | ~83% | — | ||
KOH | ||||||||
2.5M | −0.54 | 480 | 60% | 672 | 84% | — | ||
KOH | ||||||||
C/De-alloyed | 1.0M | ~−1.5 | 320 | 80% | — | — | 50 | Zhong et al. |
Cu-A1/PTFE | KOH | (2020) | ||||||
Surface | 3M | −0.68 | — | — | 336 | 84% | — | Kibria |
Reconstructed | KOH | et al. | ||||||
Cu | (2018) | |||||||
Tetrahydro- | 1.0M | −0.83 | 230 | 72% | ~261 | ~82% | — | Li et al. |
bipyridine- | KHCO3 | (2020) | ||||||
functionalized Cu | ||||||||
MEA | 0.1M | b. 3.65/5 | b. | 64% | — | — | 195 | |
KHCO3 | Cell | 384/5 | ||||||
Voltage | ||||||||
Ionomer- | 7M | −0.91 | 930 | 60% | 1210 | ~92% | — | Arquer |
coated Cu | KOH | et al. (2020) | ||||||
MEA | 0.1M | b. 3.9/x | b. | ~55% | — | — | 60 | |
KHCO3 | Cell | 550/x | ||||||
Voltage | ||||||||
Cu (100) | 7M | −0.67 | 217 | ~70% | 280 | 90% | — | Wang |
KOH | et al. | |||||||
(2020) | ||||||||
MEA | 0.15M | b. 3.7/5 | b. | ~60% | — | — | 70 | |
KHCO3 | Cell | 192/5 | ||||||
Voltage | ||||||||
Polyamine- | 1M | −0.97 | 311 | 72% | 389 | 90% | <3 | Chen |
incorporated | KOH | et al. | ||||||
Cu | 5M | −0.62 | c. — | 84% | — | — | — | (2021) |
KOH | ||||||||
10M | 0.47 | ~28 | 87% | — | — | — | ||
KOH | ||||||||
0.8:0.2Cu/Ag | 1M | −0.72 | 159 | 48.1% | 287 | 87% | 100 | She et al. |
KOH | (2020) | |||||||
MEA- | 0.5M | b. 3/1 | b. 106/1 | 48% | b. 136/1 | 62% | 150 | |
0.8:0.2Cu/Ag | KOH | |||||||
0.8:0.1Cu/ | 1M | −0.70 | 196 | 45% | 327 | 75% | — | |
Ni—N—C | KOH | |||||||
Cu/CAL | 1M | ~−1.34 | 276 | ~23% | 480 | 40% | 12.5 | Huang |
H3PO4 + | et al. | |||||||
3M | (2021) | |||||||
KCl//1M | ||||||||
H3PO4 | ||||||||
a. A few percent of the propanol is not calculated. | ||||||||
b. The denominator is the area of the electrode. | ||||||||
x. The area of the electrode is not specified. | ||||||||
c. The current density is not missing. | ||||||||
—. N/A |
Cathode: 2CO2+8H2O+12e −→C2H4+12OH− (3)
Anode: 6H2O→302+12H++12e − (4)
At the interface: 12OH−+12H+→12H2O (5)
CO2 dissolution: CO2+H2OH2CO3 (6)
E (RHE) =E (Hg/Hg
where R is the resistance between the cathode and reference electrodes measured by electrochemical impedance spectroscopy (EIS) with a frequency range from 105 Hz to 0.01 Hz at open circuit potential. For all MEA measurements, the full-cell voltages were directly presented without iR compensation.
where Nx is the number of electrons transferred for the specific product (x), F is the Faradaic constant, mx is the molar fraction of the specific product (x) determined by GC, fCO2 is the molar flow rate of the CO2, and jtotal is the total current density.
where Nx is the number of electrons transferred for the specific liquid product (x), F is the Faradaic constant, Cx is the concentration of the specific liquid product (x) determined by 1H NMR, Vx is the volume of the electrolyte, and Qtotal is the total charge.
where EOER Θ and Ex Θ are the thermodynamic potentials (vs. RHE) for OER and the electrocatalytic CO2 reduction to the product (x), respectively, FEx is the FE of the product (x), EC is the applied potentials at the cathode, and EFull-cell is the cell voltage of the MEA system.
where fx is the molar rate of the product (x) formation, t is the electrolysis reaction time, and A is the geometric area of the electrode.
ΔG=ΔE+ΔZPE−TΔS
where ΔE is the total energy difference, ΔZPE is the difference of the zero-point energy, and TΔS is the difference of entropy. Note that E(H) is half of the H2 (g) energy under 1.013 bar at 298.15K, E(H2O) is the energy of H2O (g) under 0.035 bar at 298.15 K and E(OH)=E(H2O)−E(H). The zero-point energy and entropy were corrected by calculating the vibrational frequencies through density functional perturbation theory at 298.15 K.
- 1. T. T. Zhuang, Z. Q. Liang, A. Seifitokaldani, Y. Li, P. De Luna, T. Burdyny, F. L. Che, F. Meng, Y. M. Min, R. Quintero-Bermudez, C. T. Dinh, Y. J. Pang, M. Zhong, B. Zhang, J. Li, P. N. Chen, X. L. Zheng, H. Y. Liang, W. N. Ge, B. J. Ye, D. Sinton, S. H. Yu, E. H. Sargent, Steering post-C—C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421-428 (2018). doi: 10.1038/s41929-018-0084-7;
- 2. S. C. Ma, M. Sadakiyo, R. Luo, M. Heima, M. Yamauchi, P. J. A. Kenis, One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer. J. Power Sources 301, 219-228 (2016). doi:10.1016/j.jpowsour.2015.09.124;
- 3. T. T. H. Hoang, S. C. Ma, J. I. Gold, P. J. A. Kenis, A. A. Gewirth, Nanoporous copper films by additive-controlled electrodeposition: CO2 reduction catalysis. ACS Catal. 7, 3313-3321 (2017). doi: 10.1021/acscatal.6b03613;
- 4. D. H. Nam, O. S. Bushuyev, J. Li, P. De Luna, A. Seifitokaldani, C. T. Dinh, F. P. Garcia de Arquer, Y. H. Wang, Z. Q. Liang, A. H. Proppe, C. S. Tan, P. Todorovic, O. Shekhah, C. M. Gabardo, J. W. Jo, J. M. Choi, M. J. Choi, S. W. Baek, J. Kim, D. Sinton, S. O. Kelley, M. Eddaoudi, E. H. Sargent, Metal-organic frameworks mediate Cu coordination for selective CO2 electroreduction. J. Am. Chem. Soc. 140, 11378-11386 (2018). doi: 10.1021/jacs.8b06407;
- 5. J. J. Lv, M. Jouny, W. Luc, W. L. Zhu, J. J. Zhu, F. Jiao, A highly porous copper electrocatalyst for carbon dioxide reduction. Adv. Mater. 30, 1803111 (2018). doi: 10.1002/adma.201803111;
- 6. T. T. H. Hoang, S. Verma, S. C. Ma, T. T. Fister, J. Timoshenko, A. I. Frenkel, P. J. A. Kenis, A. A. Gewirth, Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791-5797 (2018). doi: 10.1021/jacs.8b01868;
- 7. Y. G. C. Li, Z. Y. Wang, T. G. Yuan, D. H. Nam, M. C. Luo, J. Wicks, B. Chen, J. Li, F. W. Li, F. P. Garcia de Arquer, Y. Wang, C. T. Dinh, O. Voznyy, D. Sinton, E. H. Sargent, Binding site diversity promotes CO2 electroreduction to ethanol. J. Am. Chem. Soc. 141, 8584-8591 (2019). doi: 10.1021/jacs.9b02945;
- 8. C. T. Dinh, T. Burdyny, M. G. Kibria, A. Seifitokaldani, C. M. Gabardo, F. P. Garcia de Arquer, A. Kiani, J. P. Edwards, P. De Luna, O. S. Bushuyev, C. Q. Zou, R. Q. Bermudez, Y. J. Pang, D. Sinton, E. H. Sargent, CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783-787 (2018). doi:10.1126/science.aas9100;
- 9. N. Martid, C. Reller, C. Macauley, M. Löffler, B. Schmid, D. Reinisch, E. Volkova, A. Maltenberger, A. Rucki, K. J. J. Mayrhofer, G. Schmid, Paramelaconite-enriched copper-based material as an efficient and robust catalyst for electrochemical carbon dioxide reduction. Adv. Energy Mater. 9, 1901228 (2019). doi: 10.1002/aenm.201901228;
- 10. D. Anastasiadou, M. Schellekens, M. de Heer, S. Verma, E. Negro, Electrodeposited Cu2O films on gas diffusion layers for selective CO2 electroreduction to ethylene in an alkaline flow electrolyzer.
ChemElectroChem 6, 3928-3932 (2019). doi: 10.1002/celc.201900971; - 11. W. C. Ma, S. J. Xie, T. T. Liu, Q. Y. Fan, J. Y. Ye, F. F. Sun, Z. Jiang, Q. H. Zhang, J. Cheng, Y. Wang, Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C—C coupling over fluorine-modified copper. Nat. Catal. 3, 478-487 (2020). doi: 10.1038/s41929-020-0450-0;
- 12. M. Zhong, K. Tran, Y. M. Min, C. H. Wang, Z. Y. Wang, C. T. Dinh, P. De Luna, Z. Q. Yu, A. S. Rasouli, P. Brodersen, S. Sun, O. Voznyy, C. S. Tan, M. Askerka, F. L. Che, M. Liu, A. Seifitokaldani, Y. J. Pang, S. C. Lo, A. Ip, Z. Ulissi, E. H. Sargent, Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 581, 178-183 (2020). doi: 10.1038/s41586-020-2242-8;
- 13. M. G. Kibria, C. T. Dinh, A. Seifitokaldani, P. De Luna, T. Burdyny, R. Quintero-Bermudez, M. B. Ross, O. S. Bushuyev, F. P. Garcia de Arquer, P. D. Yang, D. Sinton, E. H. Sargent, A surface reconstruction route to high productivity and selectivity in CO2 electroreduction toward C2+ hydrocarbons. Adv. Mater. 30, 1804867 (2018). doi: 10.1002/adma.201804867;
- 14. F. W. Li, A. Thevenon, A. R. Hernindez, Z. Y. Wang, Y. L. Li, C. M. Gabardo, A. Ozden, C. T. Dinh, J. Li, Y. H. Wang, J. P. Edwards, Y. Xu, C. McCallum, L. Z. Tao, Z. Q. Liang, M. C. Luo, X. Wang, H. H. Li, C. P. O'Brien, C. S. Tan, D. H. Nam, R. Q. Bermudez, T. T. Zhuang, Y. G. C. Li, Z. J. Han, R. D. Britt, D. Sinton, T. Agapie, J. C. Peters, E. H. Sargent, Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509-513 (2020). doi: 10.1038/s41586-019-1782-2;
- 15. F. P. Garcia de Arquer, C. T. Dinh, A. Ozden, J. Wicks, C. McCallum, A. R. Kirmani, D. H. Nam, C. Gabardo, A. Seifitokaldani, X. Wang, Y. C. Li, F. Li, J. Edwards, L. J. Richter, S. J. Thorpe, D. Sinton, E. H. Sargent, CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2 . Science 367, 661-666 (2020). doi:10.1126/science.aay4217;
- 16. Y. H. Wang, Z. Y. Wang, C. T. Dinh, J. Li, A. Ozden, M. G. Kibria, A. Seifitokaldani, C. S. Tan, C. M. Gabardo, M. C. Luo, H. Zhou, F. W. Li, Y. W. Lum, C. McCallum, Y. Xu, M. X. Liu, A. Proppe, A. Johnston, P. Todorovic, T. T. Zhuang, D. Sinton, S. O. Kelley, E. H. Sargent, Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis. Nat. Catal. 3, 98-106 (2020). doi: 10.1038/s41929-019-0397-1;
- 17. X. Y. Chen, J. F. Chen, N. M. Alghoraibi, D. A. Henckel, R. X. Zhang, U. O. Nwabara, K. E. Madsen, P. J. A. Kenis, S. C. Zimmerman, A. A. Gewirth, Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes. Nat. Catal. 4, 20-27 (2021). doi: 10.1038/s41929-020-00547-0;
- 18. X. J. She, T. Y. Zhang, Z. Y. Li, H. M. Li, H. Xu, J. J. Wu, Tandem electrodes for carbon dioxide reduction into C2+ products at simultaneously high production efficiency and rate. Cell Rep. Phys. Sci. 1, 100051 (2020). doi: 10.1016/j.xcrp.2020.100051;
- 19. J. E. Huang, F. W. Li, A. Ozden, A. S. Rasouli, F. P. G. D. Arquer, S. J. Liu, S. Z. Zhang, M. C. Luo, X. Wang, Y. W. Lum, Y. Xu, K. Bertens, R. K. Miao, C. T. Dinh, D. Sinton, E. H. Sargent, CO2 electrolysis to multicarbon products in strong acid. Science 372, 1074-1078 (2021). doi: 10.1126/science.abg6582
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D. Anastasiadou, M. Schellekens, M. de Heer, S. Verma, E. Negro, Electrodeposited Cu2O films on gas diffusion layers for selective CO2 electroreduction to ethylene in an alkaline flow electrolyzer. ChemElectroChem 6, 3928-3932 (2019). doi: 10.1002/celc.201900971. |
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F. W. Li, A. Thevenon, A. R. Hernández, Z. Y. Wang, Y. L. Li, C. M. Gabardo, A. Ozden, C. T. Dinh, J. Li, Y. H. Wang, J. P. Edwards, Y. Xu, C. McCallum, L. Z. Tao, Z. Q. Liang, M. C. Luo, X. Wang, H. H. Li, C. P. O'Brien, C. S. Tan, D. H. Nam, R. Q. Bermudez, T. T. Zhuang, Y. G. C. Li, Z. J. Han, R. D. Britt, D. Sinton, T. Agapie, J. C. Peters, E. H. Sargent, Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509-513 (2020). doi: 10.1038/s41586-019-1782-2. |
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M. G. Kibria, C. T. Dinh, A. Seifitokaldani, P. De Luna, T. Burdyny, R. Quintero-Bermudez, M. B. Ross, O. S. Bushuyev, F. P. García de Arquer, P. D. Yang, D. Sinton, E. H. Sargent, A surface reconstruction route to high productivity and selectivity in CO2 electroreduction toward C2+ hydrocarbons. Adv. Mater. 30, 1804867 (2018). doi: 10.1002/adma.201804867. |
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T. T. H. Hoang, S. Verma, S. C. Ma, T. T. Fister, J. Timoshenko, A. I. Frenkel, P. J. A. Kenis, A. A. Gewirth, Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791-5797 (2018). doi: 10.1021/jacs.8b01868. |
T. T. Zhuang, Z. Q. Liang, A. Seifitokaldani, Y. Li, P. De Luna, T. Burdyny, F. L. Che, F. Meng, Y. M. Min, R. Quintero-Bermudez, C. T. Dinh, Y. J. Pang, M. Zhong, B. Zhang, J. Li, P. N. Chen, X. L. Zheng, H. Y. Liang, W. N. Ge, B. J. Ye, D. Sinton, S. H. Yu, E. H. Sargent, Steering post-C-C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421-428 (2018). doi: 10.1038/s41929-018-0084-7. |
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X. Y. Chen, J. F. Chen, N. M. Alghoraibi, D. A. Henckel, R. X. Zhang, U. O. Nwabara, K. E. Madsen, P. J. A. Kenis, S. C. Zimmerman, A. A. Gewirth, Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes. Nat. Catal. 4, 20-27 (2021). doi: 10.1038/s41929-020-00547-0. |
Y. G. C. Li, Z. Y. Wang, T. G. Yuan, D. H. Nam, M. C. Luo, J. Wicks, B. Chen, J. Li, F. W. Li, F. P. García de Arquer, Y. Wang, C. T. Dinh, O. Voznyy, D. Sinton, E. H. Sargent, Binding site diversity promotes CO2 electroreduction to ethanol. J. Am. Chem. Soc. 141, 8584-8591 (2019). doi: 10.1021/jacs.9b02945. |
Y. H. Wang, Z. Y. Wang, C. T. Dinh, J. Li, A. Ozden, M. G. Kibria, A. Seifitokaldani, C. S. Tan, C. M. Gabardo, M. C. Luo, H. Zhou, F. W. Li, Y. W. Lum, C. McCallum, Y. Xu, M. X. Liu, A. Proppe, A. Johnston, P. Todorovic, T. T. Zhuang, D. Sinton, S. O. Kelley, E. H. Sargent, Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis. Nat. Catal. 3, 98-106 (2020). doi: 10.1038/s41929-019-0397-1. |
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